The emerging fields of 5G and 6G telecommunication networks, Internet of Things, and artificial intelligence have intensified the demand for green nanostructured materials with adjustable and intelligent features that respond to external stimuli. By leveraging the insulator-to-metal transition of VO2 nanoparticles, responsive composite films were developed by integrating these nanoparticles within a biopolymeric network of cationic cellulose nanofibers (CNF+). These films exhibit a reversible change in GHz permittivity upon exposure to thermal or optical stimuli, facilitating dynamic control of their electrical properties. The layered structure of the films further enhances their robustness, featuring a VO2 nanoparticle core encased within CNF+ layers. This design not only strengthens the structure but also significantly boosts light-induced conductivity, particularly in layered variant, underscoring its potential in optoelectronic applications. Simulation studies reveal that the nonuniform, reconfigurable intelligent surface (RIS) of the developed mixed film adeptly manipulates incident electromagnetic waves, making it suitable for 5G/6G wireless signals. Conversely, the layered film serves as a switchable electromagnetic interference (EMI) shield, demonstrating notable differences in shielding efficiency between its hot and cold states. Consequently, CNF+/VO2 composite films designed in this work emerge as a versatile, adaptable platform for intelligent electronics, particularly in the realm of 5G/6G wireless communications.